Chlorine and/or bromine phosphonates



United States Patent New Jersey No Drawing. Filed Sept. 23, 1964, Ser.No. 398,793

19 Claims. (Cl. 260-930) This invention relates to the preparation ofnovel halogen containing organic phosphorus compounds.

It is an object of the present invention to prepare novel phosphites,phosphates, phosphonates and thiophosphates.

Another object is to prepare compounds suitable as flame proofingagents.

A further object is to prepare novel flame resistant polyurethanes.

A still further object is to introduce large amounts of aromaticallybound halogen together with phosphorus into chemical molecules.

Still further objects and the entire scope of applicability of theinvention will become apparent from the detailed description givenhereinafter, It should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingcompounds having one of the following formulae:

R3(OR4) 0P and HOR' OPOR OP K OIO HORro ORnOH I II where R is apolyhalophenyl group wherein the halogen atoms have an atomic weight of35 to 80, i.e. the halogen is chlorine or bromine, R and R arehydroxyalkyl,

R is alkylene, R and R are alkylene or hydroxyalkylene, x, y and z arezero or a positive integer, R R R and R are alkylene,alkyleneoxy-alkylene or alkylene-poly(oxyalkylene) and R is tetrahalobisphenol A or other tetrahaloalkylidene bisphenols from which thehydroxyl hydrogens have been removed and the halo atoms have an atomicweight of 35 to 80.

A specially preferred class of compounds is that of Formula I where R ispolyhalophenyl having 3 to 5 halogen atoms and R (OR O and R (OR O- areboth residues of a polyalkylene glycol, more preferably polypropyleneglycol or polyethylene glycol, most preferably dipropylene glycol. Mostpreferably R is pentachlorophenyl.

The phosphites of Formulae I and II can be converted to thecorresponding phosphates by oxidation with 1 mole of hydrogen peroxide(either 30 or 50% concentration) for each phosphorus atom, or with otherperoxy compounds, e.g. peracetic acid, or by air oxidation. They canalso be converted to the corresponding thiophosphates by heating with 1atomic weight of sulfur per phosphorus atom. They can also be convertedto the corresponding phosphonates by an Arbuzov reaction using catalyticamounts, e.g. 110% of alkyl chloride, bromide or iodide or a similarhalohydrin at elevated temperatures, Additional examples of suitablecatalysts for the Arbuzov rearrangement are set forth in Friedman Patent3,141,032, col. 1, lines 42-54.

The phosphates can also be prepared by reacting a di'(polyhalop'henyl)phosphoric acid with an alkylene oxide. Thus pentachlorophenylphosphoric acid can be reacted with ethylene oxide to givepentachlorophenyl bis(hydroxyethyl) phosphate or with propylene oxide togive pentachlorophenyl bis(hydroxypropoxypropyl) phosphates. Thepentachlorophenyl phosphoric acid can be formed by heatingpentachlorophenol with phosphoric acid. Alternatively, phenoxyphosphorus oxydichloride can be treated with chlorine to givepentachlorophenoxy phosphorus oxydichloride and the latter reacted with2 or more moles of alkylene oxide, e.g. propylene oxide to givepentachlorophenyl bis(hydroxypolypropoxypropyl) phosphate having 2, 5 or10 propoxy units in each polypropoxy group.

The phosphonates can similarly be made in alternative fashion by addingchlorine to phenyl phosphorus oxydichloride to form trichlorophenylphosphorus oxydichloride or pentachlorophenyl phosphorus oxydichloridefollowed by reaction with alkylene oxide, e.g. ethylene oxide orpropylene oxide to form bis(hydroxypropyl) trichlorobenzene phosphonateor bis(hydroxypropoxypropyl)pentachlorobenzene phosphonate, etc.

The phosphites of the present invention, as Well as the phosphates,thiophosphates and phosphonates in general are non volatile liquids andare useful as hydroxyl reactants which impart flame resistance topolyurethanes, polyesters, polyolefins, e.g. polyethylene,polypropylene, ethylene-propylene copolymer, vinyl polymers, e.g.polystyrene and vinyl acetate, acrylates and, methacrylates, e.g. methylmethacrylate polymer and ethyl acrylate polymer, neoprene, naturalrubber, butadiene-styrene copolymer, butyl rubber, etc. The phosphites,e.g. in an amount of 1% are stabilizers for vinyl chloride resins.

The phosphite compounds of Formula I of the present invention areconveniently prepared by reacting 1 mole of a hydrocarbon bis(hydroxyalkyl) phosphite, or hydrocarbon bis (hydroxyalkoxyalkyl)phosphite, or hydrocarbon bis (hydroxypolyoxyalkyl) phosphite with 1mole of a polyhalophenol. Preferably the hydrocarbon group is an arylgroup, most prefer-ably phenyl or cresyl.

The reaction to form the phosphite is preferably carried out in thepresence of a catalyst. Alkaline catalysts can be employed for thetransesterification. Preferably the catalyst has a pH of at least 11 ina 0.1 N solution. Examples of such catalysts are sodium phenate, sodiumcresylate, sodium methylate, sodium decylate, potassium phenate, sodiumpentachlorophenate, sodium 2,4,6 trichlorophenate, sodiumpentabromophenate. The catalyst is employed in an amount of 0.15% of thereactants.

There can also be used as catalysts for the transesterifi cationdihydrocarbon or dihaloaryl phosphite, e.g. 0.1-5% of diphenylphosphite, di-o-cresyl phosphite, di-p-cresyl phosphite, dimethylphosphite, didecyl phosphite, dioctadecyl phosphite, di-p-chlorophenylphosphite, di-2,4,6-trichlorophenyl phosphite, di-pentachlorophenylphosphite and di-2,4,6-tribrornophenyl phosphite.

As the halophenol reactant to form the phosphites of Formula I there canbe used 2,3-dichlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol,2,6-dichlorophenol, 3,4- dichlorophenol, 3,5-dichlorophenol,2,3-dibromophenol, 2,4-dibromophenol, 2,5-dibromophenol,2,6-dibromophen01, 3,4-dibromophenol, 3,5-dibromophenol, 2-chloro-6-br-omo-phenol, 2-brorno-3-chlorophenol, 2-chloro-3-bromophenol,2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,5 tribromophenol,2,4,6 tribromophenol, 2 bromo- 4,6 dichlorophenol, 2,4 dibromo 6chlorophenol, 2,3,4 trichlorophenol, 2,3,4 tribromophenol, 2,3,5trichlorophenol, 2,3,5 -tribromophenol, 2,3,6 trichlorophenol, 2,3,6tribromophenol, 3,4,5 trichlorophenol, 3,4,5- tri-bromophenol, 2,4,5,6tetrachlorophenol, 2,4,5,6 tetrabromophenol, 2,4 dichloro 5,6dibromophenol, 2,3,4,5-

tetrachlorophenol, 2,3,4,5 tetrabromophenol, 2,3,5,6-

tetrachlor-ophenol, 2,3,5,6 tetrabromophenol, pentachlorophenol,pentabromophenol, 2,4,6 trichloro -3,5 dibromophenol, 2,4,6 tribromo 3,5dichlorophenol. Instead of pure compounds there can be used commercialmixtures, eg of tetrachlor-ophenol or tetrabromophenol ortrichlorophenol or tribromophenol or pentachlorophen-ol containingseveral percent of less highly chlorinated phenol.

As the hydrocarbon bis (hydroxyalkyl) phosphite or similar reactantthere can be employed phenyl bis (hydroxyethyl) phosphite, phenyl bis(Z-hydroxypropyl) phosphite, phenyl bis (4-hydroxybutyl) phosphite,phenyl bis (Z-hydroxybutyl) phosphite, phenyl bis (hydroxyethoxyethyl)phosphite, phenyl bis (2-hydropropoxypropyl) phosphite, p-cresyl bis(Z-hydroxypropoxypropyl) phosphite, methyl bis (2-hydroxypropoxypropyl)phosphite, decyl bis (Z-hydroxypropoxypropyl) phosphite, phenyl bis(4-hydroxybutoxybutyl) phosphite, phenyl bis (2-hydroxybutoxybutyl)phosphite, phenyl bis (hydroxypolyethoxyethyl) phosphite where there are2, 5, 10, 50 or 80 ethoxy groups in each polyethoxy radical, phenyl bis(2-hydroxypolypropoxypropyl) phosphite where there are 2, 5, 10, 50 or80 propoxy groups in each polypropoxy radical, phenyl bis (2hydroxypolypropoxypolyethoxyethyl) phosphite where there are 10 propoxygroups in each polypropoxy radical and 7 ethoxy groups in eachpolyethoxy radical, phenyl bis (2 hydroxypolybutoxybutyl) phosphitewhere there are 2, 5, 10, 0 or 80 butoxy groups in each polybutoxyradical, phenyl bis (4-hydroxypolybutoxybutyl) phosphite where there are2, 5, 10, 50 or 80 butoxy groups in each polybutoxy radical, phenyl bis(3 hydroxypropoxypropyl) phosphite, phenyl bis (1,2,6-hexanetriol)phosphite, phenyl bis (LHT 240) phosphite (Where LHT 240 is thepropylene oxide-1,2,6- hexanetriol adduct molecular Weight 750), phenylbis (LHT 42) phosphite (where LHT 42 is the propyleneoxide-1,2,6-hexanetriol adduct molecular weight 4000),

phenyl bis (LG-56) phosphite (Where LG56 is the propyleneoxide-glycerine adduct molecular weight 3000), phenyl bis (LG168)phosphite (where LG-168 is the propylene oxide-glycerine adductmolecular weight 1000), phenyl bis (Pluracol PeP 450) phosphite (wherePluracol 'PeP 450 is the propylene oxide pentaerythritol adductmolecular weight 450), phenyl bis (Pluracol TP 400) phosphite (wherePluracol TP 400 is the propylene oxide trimethylolpropane adductmolecular Weight 400), phenyl bis (sorbitoLpropylene oxide adductmolecular weight 3000) phosphite, phenyl dipropylene glycol1,2,6-hexanetriol phosphite. As set forth in Friedman Patent 3,009,939the vast majority of the free hydroxyl groups on the hydrocarbon bis(polypropylene glycol) phosphites are secondary hydroxylgroups althoughthere are some primary hydroxyl groups also.

In order to improve flexibility of the products and to give modifiedproducts the halogenated phenols can be first reacted with :oxirane orlower alkyloxirane. One or more ethoxy, propoxy or butoxy groups canthus be introduced into the halogenated phenol before thetransesterification is carried out. Thus by using ethylene oxide,propylene oxide, or 2-ethyl ethylene oxide there can be formed startingmaterials such as pentachlorophenoxyethanol, pentabromophenoxyethanol,pentachlorophenoxypropanol-2, pentabromophenoxypropanol-2,pentachlorophenoxybutanol 2, pentachlorophenoxyethoxyethanol,pentachlorophenoxypropoxypropanol 2, pentabromophenoxypropoxy propanol2, pentabromophenoxyethoxyethanol, pentachlorophenoxypolypropoxypropanol2 (where there are 60 propoxy groups in the polyprop-oxy radical),pentachlorophenoxypolyethoxyethanol (where there are 9 ethoxy groups inthe polyethoxy radical) tetrachlorophenoxyethanol,tetrabromophenoxyethano1, dichlorodibromophenoxyethanol,tetrachlorophenoxypropanol 2, tetrachlorophenoxy propoxypropanol 2,tetrabromophenoxypropanol 2, tetrabromophenoxypropoxypropanol 2,tetrachlorophenoxypolyethoxyethanol (where there are 15 ethoxy groups inthe polyethoxy radical), tetrabrom-ophenoxypolypropoxypropanol 2 (wherethere are 5 propoxy groups in the polypropoxy radical), 2,4,5trichlorophenoxyethanol, 2,4,6' trichlorophenoxypropan-ol 2, 2,4',6'tribromophenoxypropoxypropanol 2, 2,4,5 t-richlorophenoxyethoxyethanol,2,4',5'- trichlorophenoxypolypropoxypropanol 2 (where there are anaverage of 6.8 propoxy groups in the polypropoxy radical).

Illustrative of phosphites of Formula I which are within the presentinvention are 2,4,6-tribromophenyl bis (dipropylene glycol) phosphite,2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite,2,4,5-trichlorophenyl bis (dipropylene glycol) phosphite,2,4,5-tribromophenyl bis (dipropylene glycol) phosphite,pentachlorophenyl bis (dipropylene glycol) phosphite, pentabromophenylbis (dipropylene glycol) phosphite, tetrachlorophenyl bis (dipropyleneglycol) phosphite, tetrabromophenyl bis (dipropylene glycol phosphite,2,3,4,6-tetrachlorophenyl bis (dipropylene glycol) phosphite,2,4,5,6-tetra'bromophenyl bis (dipropylene glycol) phosphite,2,4-dichlorophenyl bis (dipropylene glycol) phosphite, 2,6-dibromophenylbis (dipropylene glycol) phosphite, 2,4,6-trichloro-3,5-dibromophenylbis (dipropylene glycol) phosphite, 2,4,6- trichlorophenyl bis(tetramethylene glycol) phosphite, 2,4,6-trichlorophenyl bis(ditetramethylene glycol) phosphite, 2,4,5-trichlorophenyl bis(hexamethylene glycol) phosphite, pentachlorophenyl bis (decamethyleneglycol) phosphite, pentabromophenyl bis (2-hydroxypropyl) phos phite,2,4,5-trichlorophenyl bis (diethylene glycol) phosphite,2,4,6-trichlorophenyl bis (diethylene glycol) phosphite,2,4,6-tribromophenyl bis (diethylene glycol) phosphite,tetrachlorophenyl bis (diethylene glycol) phosphite, tetrabrornophenylbis (diethylene glycol) phosphite, pentachlorophenyl bis (diethyleneglycol) phosphite, pentabromophenyl his (diethylene glycol) phosphite,2,4,6-trichlorophenyl bis (tripropylene glycol) phosphite, 2,4,5-tri-bromophenyl bis (polypropylene glycol molecular weight 425)phosphite, tetraclorophenyl bis (polypropylene glycol molecular weight2025) phosphite, pentachlorophenyl bis (polypropylene glycol molecularweight 1025) phosphite, pentabromophenyl bis (polypropylene glycolmolecular weight 2025) phosphite, pentachlorophenyl bis (triethyleneglycol) phosphite, tetrachlorophenyl bis (polyethylene glycol molecularweight 2000) phosphite, 2,4,6-tribromophenyl bis (polyethylene glycolmolecular weight 4000) phosphite, 2,4,5-trichlorophenyl bis(glycerine-propylene oxide adduct molecular weight 1000) phosphite,2,4,6-trichlorophenyl bis (1,2,6-hexanetriol) phosphite,pentachlorophenyl bis (glycerine propylene oxide adduct molecular weight3000) phosphite, pentachlorophenyl dipropylene glycol 1,2,6-hexanetrio1phosphite, pentabromophenyl bis (pentaerythritel-propylene oxide adductmolecular weight 1000) phosphite, tetrachlorophenyl bis(sorbitol-propylene oxide adduct molecular Weight 1000) phosphite,2,4,5-trichlorophenyl bis (1,2,6-hexanetriol-propylene oxide adductmolecular weight 750) phosphite, pentachlorophenyl bis (1,2,6-hexanetriol-propylene oxide adduct molecular weight. 4000) phosphite,pentabromophenyl bis (trimethylolpropane-propylene oxide adductmolecular weight 400) phos-- phite, pentachlorophenyl bis(di-Z-ethylethylene glycol) phosphite, 2,4,6-trichlorophenoxyethyl bis(dipropylene.

glycol) phosphite, 2,4,5-trichlorophenoxyethyl bis (diethyl-- eneglycol) phosphite, 2,4,5,6-tetrachlorophenoxyethyl bis (dipropyleneglycol) phosphite, pentachlorophenoxy-- ethyl bis (dipropylene glycol)phosphite, pentabromophenoxyethyl bis (dipropylene glycol) phosphite,2,4,6- tribromophenoxyethyl bis (dipropylene glycol) phosphite,pentachlorophenoxyethyl bis (diethylene glycol) phosphite,2,4,S-trichlorophenoxyethyl bis (diethylene glycol) phosphite,tetrabromophenoxyethyl bis (diethylene glycol) phosphite,pentachlorophenoxypropyl bis (dipropylene glycol) phosphite,2,4,S-trichlorophenoxypropyl bis (dipropylene glycol) phosphite,2,4,6-trichlorophenoxypropyl bis (polyethylene glycol molecular weight1000) phosphite, tetrachlorophenoxypropyl bis (polypropylene glycolmolecular weight 2025 phosp'hite, pentachlorophenoxyethoxyethyl bis(diethylene glycol) phosphite, pentabromophenoxyethoxyethyl bis(dipropylene glycol) phosphite, 2,4,5-trichlorophenoxyethoxyethyl bis(dipropylene glycol) phosphite, 2,4,6-trichlorophenoxypropoxypropyl bis(dipropylene glycol) phosphite, 2,4,5-tribromophenoxypropoxypropyl bis(diethylene glycol) phosphite, tetrachlorophenoxy (ethyl) ethoxy (ethyl)ethyl bis (dipropylene glycol) phosphite,pentachlorophenoxypolyethoxyethyl bis (dipropylene glycol) phosphite(where there are 19 ethoxy groups in the polyethoxy radical) andpentachlorophenoxypolypropoxypropyl bis (dipropylene glycol) phosphite(where there are 9 propoxy groups in the polypropoxy radical).

Phosphates which can be made by oxidizing the phosphites of Formula I(or by other procedures as previously set forth) include2,4,6-tribromophenyl bis (dipropylene glycol) phosphate,2,4,6-trichlorophenyl bis (dipropylene glycol) phosphate,2,4,5-tribromophenyl bis (dipropylene glycol) phosphate,pentachlorophenyl bis (dipropylene glycol) phosphate, pentabromophenylbis (dipropylene glycol) phosphate, tetrachlorophenyl bis (dipropylenegly col) phosphate, tetrabromophenyl bis (dipropylene glycol) phosphate,2,4,5,6-tetrachlorophenyl bis (dipropylene glycol) phosphate,2,4-dichlorophenyl bis (diethylene gly- 7 col) phosphate,2,6-dibromophenyl bis (dipropylene glycol) phosphate,2,4,6-trichloro-3,5-dibromophenyl bis (dipropylene glycol) phosphate,2,4,6-trichlorophenyl bis (tetramethylene glycol) phosphate,2,4,5-trichlorophenyl bis (hexamethylene' glycol) phosphate,pentachlorophenyl bis (decamethylene glycol) phosphate, pentabromophenylbis (2-hydroxypropyl) phosphate, 2,4,5-trichlorophenyl bis (diethyleneglycol) phosphate, 2,4,6-trichlorophenyl bis (diethylene glycol)phosphate, 2,4,6-tribromophenyl bis (diethylene glycol) phosphate,tetrachlorophenyl bis (diethylene glycol) phosphate, tetrabromophenylbis (diethylene glycol) phosphate, pentachlorophenyl bis (diethyleneglycol) phosphate, pentabromophenyl bis (diethylene glycol) phosphate,2,4,6-trichlorophenyl bis (tripropylene glycol) phosphate,2,4,5-tribromophenyl bis (polypropylene glycol 425) phosphate,tetrachlorophenyl bis (polypropylene glycol 2025) phosphate,pentachlorophenyl bis (polypropylene glycol 1025) phosphate,pentabromophenyl bis (polypropylene glycol 2025) phosphate,pentachlorophenyl bis (triethylene glycol) phosphate, tetrachlorophenylbis (polyethylene glycol 2000) phosphate, 2,4,6-tribromophenyl bis(polyethylene glycol 4000) phosphate, 2,4,5-trichlorophenyl bis(glycerinepropylene oxide adduct molecular Weight 1000) phosphate,2,4,6-trichlorophenyl bis (1,2,6-hexanetriol) phosphate,pentachlorophenyl bis (glycerine-propylene oxide adduct molecular Weight3000) phosphate, pentachlorophenyl dipropylene glycol 1,2,6-hexanetriolphosphate, pentabromophenyl bis (pentaerythritol-propylene oxide adductmolecular weight 1000) phosphate, tetrachlorophenyl bis(sorbitolpropylene oxide adduct molecular weight 1000) phosphate,2,4,5-trichlorophenyl bis (1,2,6- hexanetriol-propy'lene oxide adductmolecular weight 750) phosphate, pentachlorophenyl bis(1,2,6-hexanetriolpropylene oxide adduct molecular Weight 4000)phosphate, pentabromophenyl bis (trimethylolpropane-propylene oxideadduct molecular weight 400) phosphate, pentachlorophenyl bis(di-Z-ethylethylene glycol) phosphate, 2,4,6- trichlorophenoxyethyl bis(dipropylene glycol) phosphate, 2,4,S-trichlorophenoxyethyl bis(diethylene glycol) phosphate, 2,4,5,6-tetrachlorophenoxyethyl bis(dipropylene glycOl) phosphate, pentachlorophenoxyethyl bis (dipropyleneglycol) phosphate, pentabromophenoxyethyl bis (dipropylene glycol)phosphate, 2,4,6-tribromophenoxyethyl bis (dipropylene glycol)phosphate, pentachlorophenoxyethyl bis (diethylene glycol) phosphate,2,4,5-trichlorophenoxyethyl bis (diethylene glycol) phosphate,

tetrabromophenoxyethyl bis (diethylene glycol) phosphate,pentachlorophenoxypropyl bis (dipropylene glycol) phosphate,2,4,S-trichlorophenoxypropyl bis (dipropylene glycol) phosphate,2,4,6-trichlorophenoxypropyl bis (polyethylene glycol 1000) phosphate,tetrachlorophenoxypropyl bis (polypropylene glycol 2025) phosphate,pentachlorophenoxyethoxyethyl bis (diethylene glycol) phosphate,pentabromophenoxyethoxyethyl bis (dipropylene glycol) phosphate,2,4,5-trichlorophenoxyethoxyethyl bis (dipropylene glycol) phosphate,2,4,6-trichlorophenoxypropoxypropyl bis (dipropylene glycol) phosphate,2,4,5-tribromophenoxypropoxypropyl bis (diethylene glycol) phosphate,tetrachlorophenoxy (ethyl) ethoxy (ethyl) ethyl bis (dipropylene glycol)phosphate, pentachlorophenoxypolyethoxyethyl bis (dipropylene glycol)phosphate (having 19 ethoxy groups in the polyethoxy radical) andpentachlorophenoxypolypropoxypropyl bis (dipropylene glycol) phosphate(having 9 propoxy groups in the polypropoxy radical).

Thiophosphates Which can be made by heating the phosphites of Formula Iwith sulfur include 2,4,6-tribromophenyl bis (dipropylene glycol)thiophosphate, 2,4,6-trichlorophenyl bis (dipropylene glycol)thiophosphate, 2,4,5-tribromop-henyl bis (dipropylene glycol)thiophosphate, pentachlorophenyl bis (dipropylene glycol) thiophosphate,pentabromophenyl bis (dipropylene glycol) thiophosphate,tetrachlorophenyl bis (dipropylene glycol) thiophosphate,tetrabromophenyl bis (dipropylene glycol) thiophosphate,2,4,5,6-tetrachlorophenyl bis (dipropylene glycol) thiophosphate,2,4-dichlorophenyl bis (diethylene glycol) thiophosphate,2,6-dibromophenyl bis (dipropylene glycol) thiophosphate,2,4,6-trichloro-3,5-dibromophenyl bis (dipropylene glycol)thiophosphate, 2,4,6-trichlorophenyl bis (tetramethylene glycol)thiophosphate, 2,4,5-trichlorophenyl bis (hexamethylene glycol)thiophosphate, pentachlorophenyl bis (decamethylene glycol)thiophosphate, pentabromophenyl bis (2-hydroxypropyl) thiophosphate,2,4,5-trichlorophenyl bis (diethylene glycol) thiophosphate,2,4,6-trichlorophenyl bis (diethylene glycol) thiophosphate,2,4,6-tribromophenyl bis (diethylene glycol) thiophosphate,tetrachlorophenyl bis (diethylene glycol) thiophosphate,tetrabromophenyl bis (diethylene glycol) thiophosphate,pentachlorophenyl bis (diethylene glycol) thiophosphate,pentabromophenyl bis (diethylene glycol) thiophosphate,2,4,6-trichlorophenyl bis (tripropylene glycol) thiophosphate,2,4,5-tribromophenyl bis (polypropylene glycol 425) thiophosphate,tetrachlorophenyl bis (polypropylene glycol 2025) thiophosphate,pentachlorophenyl bis (polypropylene glycol 1025) thiophosphate,pentabromophenyl bis (polypropylene glycol 2025) thiophosphate,pentachlorophenyl bis (triethylene glycol) thiophosphate,tetrachlorophenyl bis (polyethylene glycol 2000) thiophosphate,2,4,6-tribromophenyl' bis (polyethylene glycol 4000) thiophosphate,2,4,5-trichlorophenyl bis (glycerine-propylene oxide adduct molecularweight 1000) thiophosphate, 2,4,6-trichlorophenyl bis(1,2,6-hexanetriol) thiophosphate, pentachlorophenyl dipropylene glycol1,2,6-hexanetriol thiophosphate, tetrachlorophenyl bis(sorbitol-propylene oxide adduct molecular weight 1000) thiophosphate,2,4,5- trichlorophenyl bis (1,2,6-hexanetriol-propylene oxide adductmolecular Weight 750) thiophosphate, pentabromophenyl bis(trimethylolpropane-propylene oxide adduct molecular Weight 400)thiophosphate, 2,4,6-trichlorophenoxyethyl bis (dipropylene glycol)thiophosphate, 2,4,5- trichlorophenoxyethyl bis (diethylene glycol)thiophosphate, 2,4,5,6-tetrachlorophenoxyethyl bis (dipropylene glycol)thiophosphate, pentachlorophenoxyethyl bis (dipropylene glycol)thiophosphate, pentabromophenoxyethyl 'bis (dipropylene glycol)thiophosphate, 2,4,6-tribromophenoxyethyl bis (dipropylene glycol)thiophosphate, pentachlorophenoxyethyl bis (diethylene glycol)thiophosphate, 2,4,S-trichlorophenoxyethyl bis (diethylene glycol)thiophosphate, tetrabrornophenoxyethyl bis (diethylene glycol)thiophosphate, pentachlorophenoxypropyl bis (dipropylene glycol)thiophosphate, 2,4,5-trichlorophenoxypropyl bis (dipropylene glycol)thiophosphate, 2,4,6-trichlorophenoxypropyl bis (polyethylene glycol1000) thiophosphate, tetrachlorophenoxypropyl bis (polypropylene glycol2025) thiophosphate, pentachlorophenoxyethoxyethyl bis (diethyleneglycol) thiophosphate, pentabromophenoxyethoxyethyl bis (dipropyleneglycol) thiophosphate, 2,4,5-trichlorophenoxyethoxyethyl bis(dipropylene glycol) thiophosphate, 2,4,6-trichlorophenoxypropoxypropylbis (dipropylene glycol) thiophosphate,2,4,5-tribromophenoxypropoxypropyl bis (diethylene glycol)thiophosphate, pentachlorophenoxypolyethoxyethyl bis (dipropyleneglycol) thiophosphate (having 19 ethoxy groups in the polyethoxyradical) and pentachlorophenoxypolypropoxypropyl bis (dipropyleneglycol) thi-ophosphate (having 9 propoxy groups in the polypropoxyradical).

Phosphonates isomeric with the phosphites of Formula I which can be madein the manner set forth earlier and which are within the inventioninclude the bis (dipropylene glycol) ester of 2,4,6-tribromoben2enephosphonic acid, dipropylene glycol 2,4,6-tribromophenyl ester ofhydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) ester of2,4,6-trichlorobenzene phosphonic acid, dipropylene glycol2,4,6-tribromophenyl ester of 2-hydroxypropoXy-propane phosphonic acid,bis (dipropylene glycol) ester of 2,4,5-trichlorobenzene phosphonicacid, dipropylene glycol 2,4,5-trichlorophenyl ester of2-hydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) esterof 2,4,5-tribromobenzene phosphonic acid, dipropylene glycol2,4,5-tribromophenyl ester of 2-hydroxypropoxypropane phosphonic acid,bis (dipropylene glycol) ester of pentachlorobenzene phosphonic acid,dipropylene glycol pentachlorophenyl ester of 2-hydroXypropoxypropanephosphonic acid, bis (dipropylene glycol) ester of pentabromobenzenephosphonic acid, dipropylene glycol pentabromophenyl ester of2-hydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) esterof tetrachlorobenzene phosphonic acid, dipropylene glycoltetrachlorophenyl ester of 2-hydroxypropoxypropane phosphonic acid, bis(dipropylene glycol) ester of tetrabromobenzene phosphonic acid,dipropylene glycol tetrabromophenyl ester of 2-hydroxypropoxypropanephosphonic acid, bis (dipropylene glycol) ester of2,4,6-trichloro-3,S-dibromobenzene phosphonic acid, dipropylene glycol2,4,6-trichloro-3,S-dibromophenyl ester of 2-hydroxypropoxypropanephosphonic acid, bis (tetramethylene glycol) ester of2,4,6-trichlorobenzene phosphonic acid, tetramethylene glycol2,4,6-trichlorophenyl ester of 4-hydroxybutane phosphonic acid, bis(hexarnethylene glycol) ester of 2,4,5-trichlorobenzene phosphonic acid,hexarnethylene glycol 2,4,5-trichlorophenyl ester of 6-hydroxyhexanephosphonic acid, bis (decamethylene glycol) ester of pentachlorobenzenephosphonic acid, decarnethyL ene glycol pentachlorophenyl ester ofIO-hydroxydecane phosphonic acid, bis (Z-hydroxypropyl) ester ofpentabromobenzene phosphonic acid, Z-hydroxypropyl pentabromophenylester of 2-hydroxypropane phosphonic acid, bis (diethylene glycol) esterof 2,4,5-trichlorobenzene phosphonic acid, diethylene glycol2,4,5-trichlorophenyl ester of hydroxyethoxyethane phosphonic acid, bis(di ethylene glycol) ester of 2,4,6-trichlorobenzene phosphonic acid,diethylene glycol 2,4,6-trichloropheny1 ester of hydroxyethoxyethanephosphonic acid, bis (diethylene glycol) ester of 2,4,6-tribrornobenzenephosphonic acid, diethylene glycol 2,4,6-tribromophenyl ester ofhydroxyethoxyethane phosphonic acid, bis (diethylene glycol) ester oftetrachlorobenzene phosphonic acid, diethylene glycol tetrachlorophenylester of hydroxyethoxyethane phosphonic acid, bis (diethylene glycol)ester of tetrabromobenzene phosphonic acid, diethylene glycoltetrabromophenyl ester of hydroxyethoxyethane phosphonic acid, bis(diethylene glycol) ester of pentachlorobenzene phosphonic acid,diethylene glycol pentachlorophenyl ester of hydroxyethoxyethanephosphonic acid, bis (diethylene glycol) ester of pentabromobenzenephosphonic acid, diethylene glycol pentabromophenyl ester ofhydroxyethoxyethane phosphonic acid, bis (tripropylene glycol) ester of2,4,6-trichlorobenzene phosphonic acid, tripropylene glycol2,4,6-trichlorophenyl ester of 2-hydroxypropoxypropoxypropane phosphonicacid, bis (polypropylene glycol 425) ester of 2,4,5-tribromobenzenephosphonic acid, polypropylene glycol 425 2,4,5-tribromophenyl ester of2-hydroxypolypropoxypropane phosphonic acid (where thehydroxypolypropoxypropane group has a molecular weight of 425), bis(polypropylene glycol 2025) ester of pentabromobenzene phosphonic acid,polypropylene glycol 2025 pentabromophenyl ester of 2-hydroXy-*polypropoxypropane phosphonic acid (where the hydroxypolypropoxypropanegroup has a molecular weight of 2025), his (triethylene glycol) ester ofpentachlorobenzene phosphonic acid, triethylene glycol pentachlorophenylester of hydroxyethoxyethoxyethane phosphonic acid, bis (polyethyleneglycol 4000) ester of 2,4,6-tribromobenzene phosphonic acid,polyethylene glycol 4000 2,4,6-tribromophenyl ester ofhydroxypolyethoxyethane phosphonic acid (where thehydroxypolyethoxyethane group has a molecular weight of 4000), his(glycerinepropylene oxide adduct molecular weight 1000) ester of2,4,5-trichlorobenzene phosphonic acid, glycerine-propylene oxide adductmolecular weight 1000' 2,4,5-trichloro phenyl ester ofglycerine-propylene oxide adduct molecular weight 1000 phosphonic acid,bis (1,2,6-hexanetriol) ester of 2,4,6-trichlorobenzene phosphonic acid,1,2,6- hexanetriol 2,4,6-trichlorophenyl ester of1,6-dihydroxyhexane-Z-phosphonic acid, dipropylene glycol 1,2,6-h6X-'anetriol pentachlorobenzene phosphonic acid, 1,2,6-hexanetriolpentachlorophenyl ester of 2hydroxypropoxypropane phosphonic acid, bis(dipropylene glycol) ester of 2,4,6-trichlorophenylethane phosphonicacid, dipropylene glycol 2,4,6-trichlorophenoxyethyl ester of2-hydroxypropoxypropane phosphonic acid, bis (diethylene glycol) esterof 2,4,6-trichlorophenylethane phosphonic acid, bis (diethylene glycol)ester of 2,4,5-trichlorophenoxyethane phosphonic acid, diethylene glycol2,4,5-trichlorophenoxyethyl ester of hydroxyethoxyethane phosphonicacid, bis (dipropylene glycol) ester of tetrachlorophenoxyethanephosphonic acid, dipropylene glycol tetrachlorophenoxyethyl ester of2-hydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) esterof pentachlorophenoxyethane phosphonic acid, dipropylene glycolpentachlorophenoxyethyl ester of 2-hydroxypropoxypropane phosphonicacid, bis (dipropylene glycol) ester of pentabromophenoxyethanephosphonic acid, dipropylene glycol pentabromophenoxyethyl ester of2-hydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) esterof 2,4,6-tribrornophenoxyethane phosphonic acid, dipropylene glycol2,4,G-tribromophenoxyethyl ester of hydroxypropoxypropane phosphonicacid, bis (diethylene glycol) ester of pentachlorophenoxyethanephosphonic acid, diethylene glycol pentachlorophenoxyethyl ester ofhydroXyethoxyethane phosphonic acid, bis (diethylene glycol) ester of2,4,5-trichlorophenoxyethane phosphonic acid, di-

ethylene glycol 2,4,5-tri-chlorophenoxyethyl ester ofhydroxyethoxyethane phosphonic acid, bis (diethylene glycol) ester oftetrabromophenoxyethane phosphonic acid, diethylene glycoltetrabromophenoxyethyl ester of hydroxyethoxyethane phosphonic acid, bis(dipropylene glycol) ester of pentachlorophenoxypropane phosphonic acid,dipropylene glycol pentachlorophenoxypropyl ester ofhydroxypropoxypropane phosphonic acid, bis (dipropylene glycol) ester of2,4,5-trichlorophenoXy-propane phosphonic acid, dipropylene glycol2,4,5-trichlorophenoxypropyl ester of hydroxypropoxypropane phosphonicacid, bis (polypropylene glycol 2025) ester of tetrachlorophenoxypropanephosphonic acid, polypropylene glycol 2025 tetrachlorophenoxypropylester of hydroxypolypropoxypropane phosphonic acid (when thehydroxypolypropoxypropane group has a molecular weight of 2025), his(dipropylene glycol) ester of pentabromophenoxyethoxyethane phosphonicacid, dipropylene glycol pentabromophenoxyethoxyethyl ester ofhydroxypropoxypropane phosphonic acid, bis (diethylene glycol) ester ofpentachlorophenoxyethoxyethane phosphonic acid, diethylene glycolpentachlorophenoxyethoxyethyl ester of hydroxyethoxyethane phosphonicacid, bis (dipropylene glycol) ester ofpentachlorophenoxypolyethoxyethane phosphonic acid (where there are 19ethoxy groups in the polyethoxy radical), dipropylene glycolpentachlorophenoxypolyethoxyethyl ester of hydroxypropoxypropane (wherethere are 19 ethoxy groups in the polyethoxy radical).

Phosphites within Formula II are prepared by reacting 1 mole oftetrachlorobisphenol A or tetrabrornobisphenol A with 2 moles of ahydrocarbon bis (hydroxyalkyl) phosphite, or hydrocarbon bis(hydroxyalkoxyalkyl) phosphite or hydrocarbon bis(hydroxypolyalkoxyalkyl) phosphite. The same starting phosphites can beemployed as those used to prepare the product of Formula I. There canalso be employed the same catalysts as those set forth as suitable forpreparing the compounds of Formula I. The phosphites of Formula II canbe oxidized to the corresponding phosphates by utilizing 2 moles ofhydrogen peroxide or the other oxidizing agents set forth previously assuitable for converting the phosphites of Formula I to phosphates.Similarly thiophosphates can be prepared by heating the phosphites ofFormula II with 2 moles of sulfur. Likewise the phosphites of Formula IIcan be converted into phosphonates by Arbuzov rearrangement usingcatalytic amounts of alkyl halides or alkali metal or alkaline earthmetal halides, e.g. amyl iodide, sodium iodide, calcium iodide, butylbromide, etc.

Illustrative of phosphites of Formula II which are within the presentinvention is tetrakis (dipropylene glycol) tetrachloro (Bisphenol A)diphosphite having the formula where DPG stands for the dipropyleneglycol residue. While the halogenation of bisphenol Aresults primarilyin the 4 halogen atoms being in the 4 ortho positions to the twohydroxyl groups it will be appreciated that there can also be present aminor amount of isomers with one or more halogen atoms meta to thehydroxyl groups. Other phosphites within Formula II include tetrakis(dipropylene glycol) tetrabromo (Bisphenol A) diphosphite, tetrakis(dipropylene glycol) dichloro dibromo (Bisphenol A) diphosphite,tetrakis (tetramethylene glycol) tetrachloro (Bisphenol A) diphosphite,tetrakis (tetramethylene glycol) tetrabromo (Bisphenol A) diphosphite,tetrakis (hexamethylene glycol) tetrachloro (Bisphenol A) diphosphite,tetrakis (hexamethylene glycol) tetra bromo (Bisphenol A) diphosphite,tetrakis (decamethylene glycol) tetrachloro (Bisphenol A) diphosphite,tetrakis (decamethylene glycol) tetrabromo (Bisphenol A) diphosphite,tetrakis (2-hydroxypropyl) tetrachloro (Bis- I phenol A) diphosphite,tetrakis (diethylene glycol) tetrachloro (Bisphenol A) diphosphite,tetrakis (diethylene glycol) tetrabromo (Bisphenol A) diphosphite,tetrakis (tripropylene glycol) tetrachloro (Bisphenol A) diphosphite,tetrakis (tripropylene glycol) tetrabromo (Bisphenol A) diphosphite,tetrakis (polypropylene glycol 425) tetrachloro (Bisphenol A)diphosphite, tetrakis (polypropylene glycol 425) tetrabromo (BisphenolA) diphosphite, tetrakis (polypropylene glycol 1025 tetrachloro(Bisphenol A) diphosphite, tetrakis (polypropylene glycol 1025)tetrabromo (Bisphenol A) diphosphite, tetrakis (polypropylene glycol2025 tetrachloro (Bisphenol A) diphosphite, tetrakis (polypropyleneglycol 2025) tetrabromo- (Bisphenol A) diphosphite, tetrakis(triethylene glycol) tetrachloro (Bisphenol A) diphosphite, tetrakis(triethylene glycol) tetrabromo (Bisphenol A) diphosphite, tetrakis(polyethylene glycol 2000) tetrachloro (Bisphenol A) diphosphite,tetrakis (polyethylene glycol 2000) tetpropylene glycol) rabromo(Bisphenol A) diphosphite, tetrakis (polyethylene glycol 4000)tetrachloro (Bisphenol A) diphosphite, tetrakis (glycerine-propyleneoxide adduct 1000) tetrachloro (Bisphenol A) diphosphite, tetrakis(glycerinepropylene oxide adduct 1000) tetrabromo (Bisphenol A)diphosphite, tetrakis (glycerine-propylene oxide adduct 3000)tetrachloro (Bisphenol A) diphosphite, tetrakis (glycerine-propyleneoxide adduct 3000) tetrabromo (Bisphenol A) diphosphite, tetrakis(1,2,6-hexanetriol) tetrachloro (Bisphenol A) diphosphite, tetrakis(1,2,6- hexanetriol) tetrabromo (Bisphenol A) diphosphite, bisdipropylene glycol bis 1,2,6-hexanetriol tetrachloro (Bisphenol A)diphosphite, tetrakis (pentaerythritol-propylene oxide adduct 1000)tetrachloro (Bisphenol A) diphosphite, tetrakis(pentaerythritol-propylene oxide adduct 1000) tetrabromo (Bisphenol A)diphosphite, tetrakis (sorbitol-propylene oxide adduct 1000) tetrachloro(Bisphenol A) diphosphite, tetrakis (sorbitol-propylene oxide adduct1000) tetrabromo (Bisphenol A) diphosphite, tetrakis(1,2,6-hexanetriol-propylene oxide adduct 750) tetrachloro (Bisphenol A)diphosphite, tetrakis (1,2,6-hexanetriol-propylene oxide adduct 750)tetrabromo (Bisphenol A) diphosphite, tetrakis(1,2,6-hexanetriol-propylene oxide adduct 4000) tetrachloro (BisphenolA) diphosphite, tetrakis (l,2,6-hexanetriol-propylene oxide adduct 4000)tetrabromo (Bisphenol A) diphosphite, tetrakis(trimethylolpropane-propylene oxide adduct 400) tetrachloro (BisphenolA) diphosphite, tetrakis (trimethylolpropane-propylene oxide adduct 400)tetrabromo (Bisphenol A) diphosphite and tetrakis (Z-ethyl-ethyleneglycol) tetrachloro (Bisphenol A) diphosphite,

There are also included in the invention tetrakis (ditetrachloroZ-butylidene diphenol, tetrakis (dipropylene glycol) tetrabromoethylidene diphenol, tetrakis (diethylene glycol) tetrachloro2-butylidene diphenol, tetrakis (dipropylene glycol) tetrachloro-B-heptylidene diphenol, tetrakis (dipropylene glycol) tetrachloromethylene diphenol. The preferred compounds within Formula H are thederivatives of bisphenol A, phosphates which can be made by oxidizingthe phosphites of Formula II e.g. with two moles of hydrogen peroxide orby other procedures such as reacting tetrachloro (Bisphenol A) with bisdipropylene glycol chlorophosphate include tetrakis (dipropylene glycol)tetrachloro (Bisphenol A) diphosphates, tetrakis (dipropylene glycol)tetrabromo (Bisphenol A) diphosphate, tetrakis (dipropylene glycol)dibromo dichloro (Bisphenol A) diphosphate, tetrakis (tetramethyleneglycol) tetrachloro (Bisphenol A) diphosphate, tetrakis (hexamethyleneglycol) tetrabromo (Bisphenol A) diphosphate, tetrakis (decamethyleneglycol) tetrachloro (Bisphenol A) diphosphate, tetrakis(2-hydroxypropyl) tetrachloro (Bisphenol A) diphosphate, tetrakis(diethylene glycol) tetrachloro (Bisphenol A) diphosphate, tetrakis(diethylene glycol) tetrabromo (Bisphenol A) diphosphate, tetrakis(tripropylene glycol) tetrachloro (Bisphenol A) diphosphate, tetrakis(tripropylene glycol) tetrabromo (Bisphenol A) diphosphate, tetrakis(polypropylene glycol 425 tetrachloro (Bisphenol A) diphosphate,tetrakis (polypropylene glycol 425) tetrabromo (Bisphenol A)diphosphate, tetrakis (polypropylene glycol 1025) tetrachloro (BisphenolA) diphosphate, tetrakis (polypropylene glycol 2025) tetrachloro(Bisphenol A) diphos phate, tetrakis (polypropylene glycol 2025)tetrabromo (Bisphenol A) diphosphate, tetrakis (triethylene glycol)tetrachloro (Bisphenol A) diphosphate, tetrakis (triethylene glycol)tetrabromo (Bisphenol A) diphosphate, tetra kis (polyethylene glycol2000) tetrachloro (Bisphenol A) diphosphate, tetrakis (polyethyleneglycol 4000) tetrachloro (Bisphenol A) diphosphate, tetrakis(polyethylene glycol 4000) tetrabromo (Bisphenol A) diphosphate,tetrakis (glycerine-propylene oxide adduct 1000) tetrachloro (BisphenolA) diphosphate, tetrakis (glycerine propylene oxide adduct 3000)tetrabromo (Bisphenol A) diphosphate, tetrakis (1,2,6-hexanetriol)tetrachloro 11 (Bisphenol A) diphosphate, tetrakis(pentaerythritolpi'opylene oxide adduct 1000) tetrachloro (Bisphenol A)diphosphate, tetrakis (sorbitol-propylene oxide adduct 1000) tetrabromo(Bisphenol A) diphosphate, tetrakis (1,2,6-hexanetriol-propylene oxideadduct 750) tetrabromo (Bisphenol A) diphosphate, tetrakis(1,2,6-hexanetriol-propylene oxide adduct 4000) tetrachloro (BisphenolA) diphosphate, and tetrakis (trimethylolpropane-propylene oxide adduct400) tetrachloro (Bisphenol A) diphosphate, tetrakis (dipropyleneglycol) tetrachloro oxyethane group has a molecular weightof 4000), thediphosphonate prepared by Arbuzov rearrangement of tetrakis(glycerine-propylene oxide adduct 1000) tetrachloro (Bisphenol A)diphosphite, the diphosphonate prepared by Arbuzov rearrangement oftetrakis (1,2,6- heXaneti-iol-propylene oxide adduct 750) tetrabromo(Bisphenol A) diphosphite, the diphosphonate prepared by Arbuzovrearrangement of tetrakis (sorbitol-propylene oxide adduct 1000)diphosphite, bis (hydroxypropoxypropane) bis (dipropylene glycol)tetrachloro (Z-butyli- 2-butylidene diphenol. dene diphenyl)diphosphonate.

Thiophosphates which can be made by reacting two Unless otherwise statedall parts and percentages are moles of sulfur with the phosphites ofFormula II include by weight. tetrakis (dipropylene glycol) tetrachloro(Bisphenol A) Example 1 dithiophosphate, tetrakis (dipropylene glycol)tetrabromo (Bisphenol A) dithiophosphate, tetrakis (dipropylene 390 i (1mole) of phenyl bls (dlpropylene glycol.) glycol) dichloro dibromo(Bisphenol A) dithiophosphate, phosphlte 330 parts (1 mole)of,recrystalhzed tetrakis (tetramethylene glycol) tetrachloro (BisphenolPromophenol and 9 P of Phenate. w A) dithiophosphate, tetrakis(hexamethylene glycol) Jected to vacuum distillation. Terminalconditions were tetrabromo (Bisphenol A) dithiophosphate, tetrakis and 392 Parts of phenol were remolled (decamethylene glycol) tetrachloro(Bisphenol A) distillate. The residue was 2,4,6-tr bromophenyl bis (d1-thiophosphate, tetrakis (diethylene glycol) tetrachloro Propylene Y'P pphite, a light yellow l1ql112d5 of (Bisphenol A) dithiophosphate,tetrakis (diethylene glymedl'um Ylscoslty' It had a refractlve Index 1of col) tetrabromo (Bisphenol A) dithiophosphate, tetrakis 3 and numberof and hydroxyl numbe of 175 (tripropylene glycol) tetrachloro(Bisphenol A) dithio- 25 (t wry 178)' 1 phosphate, tetrakis(polypropylene glycol 425) tetrabromo Examp e 2 (Bisphenol A)dithiophosphate, tetrakis (polypropylene 390 parts (1 mole) phenyl bis(dipropylene, glycol) glycol 2025) tetrachloro (Bisphenol A)dithiophosphate, phosphite, 197 parts (1 mole) of recrystallized 2,46tri tetmkis (triethylene glycol) tetrabromo (Bisphenol A) chlorophenoland 10 parts of sodium phenate were subdithiophosphate tetrakis(Polyethylane glycol 2000) jected to vacuum distillation. Terminalconditions were tetrachloro (BisphenolA) dithiophosphate, tetrakis(polyand 3 tom 90 parts of phenol wfire removed ethylene glycol 4900)tetrabfomo (BiSPhen1 A) dithio distillate. The residue was2,4,6-trichlorophenyl bis (di- 2 0.58 d kis (sorbitol-propylene oxideadduct 1000) tetrabromo g g gg jg i er 0 an y roxy num (Bisphenol A)dithiophosphate, tetrakis (pentaerythritolpropylene oxide adduct 1000)tetrachloro (Bisphenol A) Example 3 dithiophosphate, tetrakis(1,2,6-hexanetriol-propylene oxide adduct 750 tetrabromo (Bisphenol A)dithiophos- Pans of R P bls (dlPrPpylene glycol) PhOSPhlte, phate, andtetrakis (trimethylolpropane propylene Oxide 40 197. parts ofredistilled 2,4,5 trichlorophenol and 10 parts adduct 400) tetrachloro(Bisphenol A) dithiophosphate of sodium phenate were sub ected to vacuumdistillation.

Phosphonates isomeric with the phosphites of Formula Termmal Condmonswere 135 and 5 parts H which can be madc by Arbuzov rearrangement of ofphenol were removed as distillate. The residue was phosphites of FormulaII and which are within the inbis (d@pr0Py 1ene glycol) phosphite,Vention include his (hydroxypropoxypmpane) bis light yellow liquid ofmed um viscosity having a refracpropylene glycol) t t hl (Bi h l A) di hh tive index of 1.5140, an acid number of 0.12 and a hynate having theformula droxyl number of 226 (theory 228).

CH3 CH3 01 G1 l (IJHS |3Ha 5 CH G1 oomoHoOHiCHOH HooHoHiooHomo CH3 CH3bis (hydroxypropoxypropane) bis (dipropylene glycol) tetrabromo(Bisphenol A) diphosphonate, bis (4-hydroxybutane) bis (tetramethyleneglycol) tetrachloro (Bisphenol A) diphosphonate, bis (IO-hydroxydecane)bis (decamethylene glycol) tetrabromo (Bisphenol A) cliphosphonate, bis(hydroxyethoxyethane) bis (diethylene glycol) tetrachloro (Bisphenol A)diphosphonate, bis (hydroxyethoxyethane) bis (dicthylene glycol)tetrabromo (Bisphenol A) :diphosphonate, bis (Z-hydroxypropane) bis(hydroxypropyl) tetrachloro (Bisphenol A) diphosphonate, bis(hydroxypropoxy-propoxypropane) bis (tripropylene glycol) tetrachloro(Bisphenol A) diphosphonate, bis (hydroxypolypropoxypropane) bis(polypropylene glycol 2025) tetrachloro (Bisphenol A) diphosphonate(where the polypropoxypropane group has a molecular weight of 2025 bis(hydroxyethoxyethoxyethane) bis (triethylene glycol) tetrabromo(Bisphenol A) diphosphonate bis (hydroxypolyethoxyethane) bis(polyethylene glycol 4000) tetrachloro (Bisphenol A) diphosphonate(where the hydroxypolyethphosphite.

Example 4 The procedure of Example 1 was repeated replacing the2,4-6-tribromophenol by 1 mole of pentabromophenol to producepentabromophenyl bis (dipropylene glycol) phosphite.

Example 5 Example 7 The procedure of Example 1 was repeated replacingthe phenyl bis (dipropylene glycol) phosphite by 1 mole of phenyl bis(diethylene glycol) phosphite to produce 2,4,6-tribromophenyl bis(diethylene glycol) phosphite.

Example 8 The procedure of Example 2 Was repeated replacing the phenylbis (dipropylene glycol) phosphite by 1 mole of phenyl bis (diethyleneglycol) phosphite to produce 2,4,6-trichlorophenyl bis (diethyleneglycol) phosphite.

' Example 9 The procedure of Example 3 was repeated replacing the phenylbis (dipropylene glycol) phosphite by 1 mole of phenyl bis(polypropylene glycol 2025) phosphite to produce 2,4,5-trichlorophenylbis (polypropylene glycol 2025 phosphite.

Example 10 The procedure of Example 2 was repeated replacing the phenylbis (dipropylene glycol) phosphite by 1 mole of phenyl bis(l,2,6-hexanetriol-propylene oxide adduct 750) phosphite to produce2,4,6-t1'ichlorophenyl bis (1,2,6- hexanetriol-propylene oxide adduct750) phosphite.

Example 11 The procedure of Example 1 was repeated replacing the2,4,6-tribromophenol by 1 mole of 2,4,6-tribromophenoxyethanol toproduce 2,4,6-tribromophenoxyethyl bis (dipropylene glycol) phosphite.

Example 12 I The procedure of Example 2 was repeated replacing the2,4,6-trichlorophenol by 1 mole of 2,4,6-trichlorophenoxyethanol bis(dipropylene glycol) phosphite.

Example 13 p 1 mole of 50% aqueous hydrogen peroxide was stirred into 1mole of 2,4,6-tribromophenyl bis (dipropylene glycol) phosphite. Afterreaction was complete, the water was distilled off leaving a residue of2,4,6-tribromophenyl bis (dipropylene glycol) phosphate.

Example 14 1 mole of 50% aqueous hydrogen peroxide was stirred into 1mole of 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite. Afterreaction was complete the water was distilled off leaving a residue of2,4,6-trichlorophenyl bis (dipropylene glycol) phosphate. In similarfashion there were prepared 2,4,6-trichlorophenyl bis (diethyleneglycol) phosphate and 2,4,6-trichlorophenoxyethyl bis (dipropyleneglycol) phosphate from the corresponding phosphites.

Example 15 1 mole of 50% aqueous hydrogen peroxide was stirred into 1mole of pentachlorophenyl bis (dipropylene glycol) phosphite. Afterreaction was complete the water was distilled olf leaving a residue ofpentachlorophenyl bis (dipropylene glycol) phosphate.

Example 16 To 1 mole of 2,4,6-trichlorophenyl bis (dipropylene glycol)phosphite there was added 1 mole of sulfur. The mixture was heated to130 C. until reaction was complete. The product was2,4,6-trichlorophenyl bis (dipropylene glycol) thiophosphate.

Example 17 1 mole of 2,4,6-trichlorophenyl bis (dipropylene glycol)phosphite was heated with mole percent of n-butyl bromide at 125-135 C.for 8 hours. Volatile material was stripped off at 150 C. and mm. Theliquid residue was essentially 2,4,6-trichlorophenyl dipropylene glycolhydroxypropoxypropane phosphonate containing a very small amount oftrichlonophenyl dipropylene glycol butane phosphonate.

14 Example 18 Example 19 The procedure of Example 17 was repeatedreplacing the 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphiteby 1 mole of 2,4,5-trichlorophenyl bis (diethylene glycol) phosphite toproduce 2,4,5-trichlorophenyl diethylene glycol hydroxyethoxyethanephosphonate.

Example 20 The procedure of Example 17 was repeated replacing the2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite by2,4,6-trichlorophenyl bis (hexamethylene glycol) phosphite to produce2,4,6-trichlorophenyl hexamethylene glycol 6-hydroxyhexane phosphonate.

Example 21 2 moles of dipropylene glycol were heated at 160 C. in areceptacle equipped with a condenser and 1 mole of 2,4,5-trichlorophenylphosphorus oxydichloride was added dropwise over a period of one hourand the mixture maintained at 160 C. for 5 hours. The hydrogen chlorideformed was removed as a gas and the residue was the bis (dipropyleneglycol) ester of 2,4,5-trichlorobenzene phosphonic acid.

7 Example 22 2 moles of phenyl bis (dipropylene glycol) phosphite, 1mole of tetrachloro (Bisphenol A) and 10 parts of sodium phenate weresubjected to vacuum conditions. Terminal conditions were C. and 3 torr.182 parts of phenol were removed as distillate. The liquid residue wastetrakis (dipropylene glycol) tetrachloro (Bisphenol A) diphosphite,hydroxyl number 232, also called tetrakis (dipropylene glycol)tetrachloro isopropylidene diphenol.

Example 23 The procedure of Example 22 was repeated replacing thetetrachloro (Bisphenol A) by 1 mole of tetrabromo (Bisphenol A) toproduce tetrakis (dipropylene glycol) tetrabromo (Bisphenol A)diphosphite, hydroxyl number 197.

Example 24 The procedure of Example 22 was repeated replacing the phenylbis (dipropylene glycol) phosphite by 2 moles of phenyl bis(hexamethylene glycol) phosphite to produce tetrakis (hexamethyleneglycol) tetrachloro (Bisphenol A) diphosphite.

Example 25 The procedure of Example 22 was repeated replacing the phenylbis (dipropylene glycol) phosphite by 2 mols of phenyl bis (diethyleneglycol) phosphite to produce tetrakis (diethylene glycol) tetrachloro(Bisphenol A) diphosphite.

Example 26 The procedure of Example 22 was repeated replacing the phenylbis (dipropylene glycol) phosphite by 2 moles of phenyl bis(polypropylene glycol 2025) phosphite to produce tetrakis (diethyleneglycol) tetrachloro (Bisphenol A) diphosphite.

1 5 Example 27 2 moles of 50% aqueous hydrogen peroxide were stirredinto 1 mole of tetrakis (dipropylene glycol) tetrachloro (Bisphenol A)diphosphite. After reaction was complete, the water was distilled offleaving a liquid residue of tetrakis (dipropylene glycol) tetrachloro(Bisphenol A) diphosphate.

Example 28 To 1 mole of tetrakis (dipropylene glycol) tetrachloro(Bisphenol A) disphosphite there was added 2 moles of sulfur. Themixture was heated to 130 C. until reaction was complete. The productwas tetrakis (dipropylene glycol) tetrachloro (Bisphenol A)dithiophosphate.

Example 29 1 mole of tetrakis (dipropylene glycol) tetrachloro(Bisphenol A) diphosphite was heated with 5 mole percent of n-butylbromide at 125135 C. for hours.

Volatile material was stripped off at 150 C. and 10 mm. a

The liquid residue was essentially bis (hydroxypropoxypropane) bis(dipropylene glycol) tetrachloro (Bisphenol A) diphosphonate.

As has been set forth previously the phosphite, phosphate, thiophosphateand phosphonate products of the present invention are specially usefulin preparing polyurethanes. It has been observed for example that theproducts of the present invention, particularly those containing a trito pentahalophenyl group (as well as those which aretetrahaloisopropylidenediphenol derivatives), have outstandingresistance to burning. Thus a polyurethane made from toluenediisocyanate and 2,4,6-trichlorophenyl bis (dipropylene glycol)phosphite would not burn when subjected to a flame in either thevertical or horizontal position. This was true even when a portion ofthe 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite wasreplaced in part by a less flame resistant polyol.

The phosphites, phosphates, thiophosphates and phosphonates can be thesole hydroxyl reactant present or they can be used in admixture withother polyhydroxy compounds (polyols) in forming the polyurethanes.Foamed polyurethanes can be obtained by adding water prior to orsimultaneously with the addition of the polyisocyanate.

Alternatively, foams can be prepared by uniformly distributing aliquefied halogen substituted alkane containing at least one fluorineatom in its molecule and having a boiling point at one atmospherepressure not higher than 80 F. and preferably not lower than 60 F. ineither the phosphite (or mixture of phosphite and other polyhydroxycompound) reactant or the polyisocyanate reactant and then mixing thereactants and permitting the temperature of the mixture to rise duringthe ensuing reaction above the boiling point of the liquefied gas toproduce a porous polyurethane. Such fluorine containing compoundsinclude dichlorodifluoromethane, dichloromonofluoromethane,chlorodifluoromethane, and dichlorotetrafluoroethane. The foams can beformed with such fluorine containing compounds in the manner describedin General Tire British Patent 821,342.

Foamed polyurethanes can be made by either the one shot or two stepprocedures. In the case of the reaction of phosphites having a hydroxylnumber above 125 in order to form a good flexible foam it is oftendesirable to employ the two step procedure unless an additionalpolyhydroxy reactant is added to lower the hydroxyl number of thehydroxy reactants to below 125 and preferably below 100, e.g., as low as25, but preferably at least 35.

In preparing urethane foams according to the invention a rigid foam ismade utilizing a polyol phosphite of the type set forth supra (ormixture of such phosphite and another polyhydroxy containing compound)having a hydroxyl number of 350-750; a semi-rigid foam is pre- 1% paredif the hydroxyl number is 75-350, and a flexible foam is prepared if thehydroxyl number is 35-75.

The polyurethanes prepared according to the present invention aresolids. They have good flame-proofing properties and in the foamed formare useful as linings for textiles, e.g., coats, suits and dresses,insulation in building construction, upholstery filling material,pillows, hair curlers, brushes, carpet underlays or backings, shockabsorbent filling for packages, shoes, etc.

The unfoamed polyurethane products are useful wherever elastomericpolyurethanes can be employed with the advantage of improved flame andfire resistance. The elastorners in thread form can be employed inmaking girdles. The unfoamed polyurethanes are suitable for molding cupsand other articles, and as protective coatings for steel, wood and glassand as adhesives.

As examples of organic polyisocyanates which can be used to make thepolyurethanes there can be employed toluene-2,4-diisocyanate;toluene-2,d-diisocyanate; 4-methoxy-1,3-phenylene diisocyanate; diphenylmethane-4,4- diisocyanate; 4-chloro-1,3-phenylene diisocyanate;4-isopropyl-1,3-phenylene diisocyanate; 2,4-diisocyanato-diphenylether;3,3 dimethyl 4,4'-diisocyanato diphenyl methane; mesitylenediisocyanate; durylene diisocyanate; 4,4-methylene bis(phenylisocyanate); benzidine diisocyanate; 4,4-diisocyanato dibenzyl;3,3'-bitolylene-4,4'-diisocyanate; 1,5-naphthylene diisocyanate;tet-ramethylenediisocyanate; hexamethylene diisocyanate; decamethylenediisocyanate; toluene-2,4,6-triisocyanate; tritolylmethanetriisocyanate, 2,4,4'-triisocyanato diphenyl ether; phenylenediisocyanate; 0-, mand p-xylene diisocyanates. The reaction product oftoluene diisocyanate with trimethylolpropane at an NCO/ OH ratio of 2:1, (Mondur CB); the the reaction product of toluene diisocyanate with1,2,6- hexanetriol at an NCO/ OH ratio of 2: 1; the reaction product oftoluene diisocyanate with a polyol phosphite at an NCO/OH ratio of 2:1,e.g., when the polyolphosphite is dipropylene glycol tetrol diphosphiteor tris (dipropylene glycol) phosphite or 2,4,6-trichlorophenyl bis(dipropylene glycol) phosphite; as well as polyisocyanates listed inSiefken (Annalen Vol. 562, pages 122-135, 1949).

There can also be used polymethylene polyphenylisocyanate molecularweight 380 to 400, having an isocyanate equivalent of 135 (maximum), aviscosity of 400 centipoises (maximum) at 25 C., a NCO content of 31%(minimum), an acid value (p.p.m. of H+) of 200 (maximum). This materialis sold commercially under the trademark PAPI. There can also be usedbitolylene diisocyanate (TODI) and dianisidine diisocyanate (DADI).

PAPI is particularly useful in forming rigid polyurethane foams as istoluene diisocyanate.

Alternatively, as the polyisocyanate there can be used prepolymers madeby reacting one or more of the above polyisocyanates with a polyhydroxycompound such as a polyester having terminal hydroxyl groups, apolyhydric alcohol, glycerides, hydroxy containing glycerides, etc. Theprepolymers should have terminal isocyanate groups. To insure this it isfrequently desirable to employ an excess of 5% or more of thepolyisocyanate in forming the prepolymer.

Typical examples of such prepolymers having isocyanate end groups arethose formed from toluene diisocyanate and polyhydroxy compounds. Unlessotherwise indicated, in the illustrative examples a mixture of 2,4-isomer and 20%, 2,6-isomer of toluene diisocyanate was employed inmaking the prepolymer. Thus, there can be used the prepolymers fromtoluene diisocyanate and castor oil, toluene diisocyanate and blown tungoil (or blown linseed oil or blown soya oil), toluene diisocyanate andthe polyester of ethylene glycol, propylene glycol and adipic acidhaving a molecular weight of 1900 described in Example I of Kohrn Patent2,953,839, as well as the isocyanate terminated prepolymers in ExamplesII-VIII, inclusive, of the Kohrn patent, toluene diisocyanate and pytetramethylene glycol (1000 molecular weight), toluene diisocyanate andpolypropylene glycol (molecular weight 2025 toluene diisocyanate anddipropylene glycol, toluene diisocyanate and polypropylene glycol(molecular weight 1025), toluene diisocyanate and LG-56(glycerine-propylene oxide adduct having a molecular weight of 3000),toluene diisocyanate and l,2,6-hexanetriol-propylene oxide adductshaving molecular weights of 500, 700, 1500, 2500, 3000 and 4000,hexamethylene diisocyanate and pentaerythritol, toluene diisocyanate andpolyethylene sebacate, toluene diisocyanate and a mixture of 98%polypropylene glycol (molecular weight 1900) with 2% 1,2,6- hexanetriol,toluene diisocyanate and a copolymer of ethylene oxide and propyleneoxide having a molecular weight of 2020, toluene diisocyanate andglyceryl adipate phthalate polymer, toluene diisocyanate and a mixtureof polypropylene ether glycol molecular weight 995 and castor oil asdescribed in Example 2 of Kane Patent 2,955, 091, as well as the otherprepolymers set forth in Examples 1 and 3-11 of Kane, toluenediisocyanate and polypropylene ether glycol (molecular weight 1800) ofExample I of Swart Patent 2,915,496 and the prepolymers of Examples II,III, VI and VIII of the Swart patent. Toluene diisocyanate and tris(dipropylene glycol) phosphite; toluene diisocyanate and tris(polypropylene glycol 2025) phosphite.

As previously stated the polyol phosphites, phosphates, thiophosphatesand phosphonates of the present invention can be the sole hydroxy-lreactant present or they can be used in admixture with other polyhydroxycompounds in forming the polyurethanes. Examples of such compounds arepolyethylene glycols having molecular weights of 400 to 3000;polypropylene glycols having molecular weights of 400 to 3000; ethyleneglycol; diethylene glycol; triethylene glycol; propylene glycol;dipropylene glycol; tripropylene glycol; thiodiglycol; glycerol;trimethylolethane; trimethylolpropane; ether triols from glycerine andpropylene oxide having molecular weights of 1000 and 3000, ethercontaining triols from 1,2,6-hexane triol and propylene oxide havingmolecular weights of 750, 1500, 2400 and 4000; sorbitol-propylene oxideadduct molecular weight 1000; pentaerythritol-propylene oxide adductmolecular weight 1000; trimethylolphenol; octakis (2-hydrox ypropyl)sucrose, pentaerythritol; castor oil; blown linseed oil; blown soya oil;N,N,N,N-tetrakis (2-hydroxypropylene) ethylene diamine; mixed ethyleneglycol-propylene glycol adipate resin molecular weight 1900;polyneopentylene sebacate; reaction product of 1 mole oftrimethylolpropane with .3000 to 12,000 molecular weight units of1,4-butanediol adipic acid polyester; oxypropylated p-tert.butylphenol-formaldehyde resin of Example 2b of De Groote United StatesPatent 2,499,365; tris (dipropylene glycol). phosphite; tris(polypropylene glycol 2025) phosphite; dipropylene glycol tetroldiphosphite; dipropylene glycol hydroxypropoxypropane phosphonate; pentahydroxyethyl' dextrose; bis polypropylene glycol 2025 ester ofhydroxypolypropoxypropane phosphonic acid (wherein thehydroxypolypropoxypropane group has a molecular weight of about 2025);his diethylene glycol ester of hydroxyethoxyethane phosphonic acid, bistripropylene glycol ester of butanephosphonic acid.

From 5 to 100% by weight of the hydroxyl component can be the phosphiteof Formula I or II (or the corresponding phosphate, thiophosphate orphosphonate).

The polyol phosphites also can be employed as light stabilizers forpolyurethane resins made from any of the non phosphite containingpolyols set forth above. For such use the polyol phosphite is employedin an amount of from 0.1-% by weight of the polyol, e.g. 2.5% by weightof 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite is added to14.4 grams of LG-56 (glycerinepropylene oxide adduct molecular weight3000) and there is added 5.2 grams of toluene diisocyanate and 0.37 gramof water to form a light stable foamed polyurethane. The phosphites oftheinven-tion not only act to stabilize the non phosphite containingpolyol employed as well as the polyurethane product but also serve asreactants.

In preparing the cured and/or foamed polyurethanes any of theconventional catalysts can be employed, e.g. sodium hydroxide, sodiummethylate, sodium phenolate, tertiary amines, (e.g. N-methyl morpholine,N-ethyl morpholine, 1,2,4-trimethylpiperazine) trimethyl amine, triethylamine, tributyl amine and other trialkyl amines. The esterificationproduct of 1 mole of adipic acid and 2 moles of diethyl ethanolamine,triethyl amine citrate, 3 morpholino-propionamide, 2diethylaminoaceta-mide, triethylene diamine, N,N,N',N' tetrakis (2hydroxypropyl) ethylene diamine, tribenzyl amine,N,N'-dimet-hylpiperazine, N,N dimethyl hexahydroaniline,2,2,1-diazabicyclooctane, 1,2-dimethylimidazole, arsenic trichloride,antimony pentachloride, titanium tetrachloride, dioctyl lead diacetate,octylene glycol titanate. There can also be used tin compounds having atleast one direct carbon to tin valence bond, e.g. hydrocarbon tinacylates such as dibutyltin dilaurate, dibutyltin dioctoate, tributyltinmonolaurate, dimethyltin diacetate, dibutyltin maleate, hydrocarbon tinalkoxides, e.g. dibutyltin diethoxide and dibutyltin dimethoxide, octylstannoic acid, trimethyltin hydroxide, trimethyltin chloride,triphenyltin hydride, triallyltin chloride, tributyltin fluoride,dibutyltin dibromide, bis (carboethoxymethyl) tin diiodide, tributyltinchloride, trioctyltin acetate, butyltin trichloride, octyltin tris(thiobutoxide), dimethyltin oxide, stannous octanoate, dioctyltin oxide,diphenyltin oxide, stannous oleate as well as the other tin compoundsset forth in Hostettler French Patent 1,212,252 and Barnes United StatesPatent 3,022,256.

There can also be used a small amount, e.g. 0.001 to 10% by weight ofthe total ingredients of a stabilizing or thickening agent, e.g.methoxylated cellulose, ethyl cellu- I lose, hydroxyethyl cellulose,benzyl cellulose, cellulose acetate, cellulose acetate-butyrate,hydroxyethyl polyvinyl alcohol, polyvinyl chloride, polymerized methylmethacrylate.

Fillers can be added in amounts up to 20% by weight, e.g. clay,diatomaceous earth, powdered aluminum and beryllium, vermiculite, cork,bark, foamed polystyrene, foamed polyethylene and foamed polypropylenecan be used.

Conventional surfactants can be added in an amount of 0.1-5% by weightof the composition. Preferably less than 1%, e.g. 0.2% of surfactant isemployed. The preferred surfactants are silicones, e.g. polydimethylsiloxane having a viscosity of 3 to 1000 centistokes, trimethoxydimethylpolysil-oxane molecular weight 850 copolymerized with adimethoxypolyethylene glycol of molecular weight 750 as well as any ofthe other siloxanes disclosed in Hostettler French Patent 1,212,252 andthe siloxaneoxyalkylene copolymers having from about 10 to by weight ofsiloxane polymer and from to 20% by weight of alkylene oxide polymersuch as the copolymers described in United States Patent 2,834,748.

Unless otherwise indicated, all parts and percentages are by weight.

In the following examples, unless otherwise indicated, when toluenediisocyanate was employed it was a mixture of 80% of the 2,4-isomer and20% of the 2,6-isomer.

In preparing one shot foams in the examples there was utilized thefollowing standard formulation:

Gram Water 0.37 Dibutyltin dilaurate 0.07 Polydimethyl siloxane (50centistokes grade) 0.12 N-ethyl morpholine 0.1

Polyol, as indicated.

This mixture is designated in the examples as Formulation A.

19 Example 30 The polyol used in Formulation A was 4.6 grams of2,4,6-tribromophenyl bis (dipropylene glycol) phosphite. Upon additionof 5.2 grams of toluene diisocyanate there was produced a solid foamwhich was non burning.

Example 31 The polyol used in Formulation A was 3.5 grams of2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite. Upon additionof 5.2 grams of toluene diisocyanate there was produced a solid foamwhich was non burning.

Example 32 The polyol used in Formulation A was 4 grams ofpentachlorophenyl bis (dipropylene glycol) phosphite. Upon addition of5.2 grams of toluene diisocyanate there was produced a solid foam whichwas non burning.

Example 33 The polyol used in Formulation A was 3.5 grams of tetrakis(dipropylene glycol) tetrachloro (Bisphenol A) diphosphite. Uponaddition of 5.2 grams of toluene diisocyanate there was produced a solidnon burning foam.

Example 34 The polyol used in Formulation A was 3.4 grams of2,4,6-trichlorophenyl bis (dipropylene glycol) phosphate. Upon additionof 5.2 grams of toluene diisocyanate there was produced a solid nonburning foam. A similar result was obtained by replacing the2,4,6-trichloropheny1 (dipropylene glycol) phosphate by2,4,6-trichlorophenyl (dipropylene glycol) thiophosphate.

Example 35 The polyol used in Formulation A was 3.5 parts of2,4,6-trichlorophenyl dipropylene glycol hydroxypropoxypropanephosphonate. Upon addition of 5.2 grams of toluene diisocyanate therewas produced a solid foam which was non burning.

Example 36 The polyol used in Formulation A was a mixture of 1.8 gramsof 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphite and 7 gramsof LG-56 (glycerine-propylene oxide adduct molecular weight 3000). Up naddition of 5.2 grams of toluene diisocyanate there was produced a solidnon burning foam.

Example 37 The polyol used in Formulation A was a mixture of 2 grams ofpentachlorophenyl bis (dipropylene glycol) phosphite and 7 grams ofpolypropylene glycol molecular weight 2025. Upon addition of 7.5 gramsof 4,4'-diphenyl methane diisocyanate there was produced a solid foamwhich was non burning.

In the following examples there was employed Formulation B whichconsisted of Polyol, as indicated. Grams Polydimethyl siloxane (Ocentistokes) 1 Dibutyltin dilaurate 0.03

Tetramethylbutane diamine 1.5

Trichlorofluoromethane 37.5

Example 38 The polyol used in Formulation B was a mixture of 46 grams ofoctakis (Z-hydroxypropyl) sucrose (molecular weight 800, hydroxyl No.560) and 105 grams of 2,4,6- trichlorophenyl bis (dipropylene glycol)phosphite. The mixture was kept at 15 C. and there was added 118.5 gramsof 4,4'-diphenylmethane diisocyanate. An exothermic reaction ensued toform a solid, non burning foam.

Example 39 The polyol used in Formulation B was a mixture of 67 grams ofoctakis (Z-hydroxyprOpyl) sucrose (hydroxyl No. 560) and 54.4 grams of2,4,6-triohlorophenyl dipropylene glycol hydroxypropoxypropanephosphonate. This mixture was kept at 15 C. and there was added 81.8grams of toluene diisocyanate. An exothermic reaction ensued to form asolid, non burning foam.

Example 40 The polyol used in Formulation B was a mixture of 67 grams of'octakis (2-hydroxypropyl) sucrose (hydroxyl No. 560), 27.1 grams of2,4,5-trichlorophenyl bis (dipropylene glycol) phosphite and 15.7 gramsof his (dipropylene glycol) hydroxypropoxypropane phosphonate. Thismixture was kept at 15 C. and there was added 118.5 grams of4,4'-diphenylmethane diisocyanate. An exothermic reaction ensued to forma solid, non burning foam. Similar results were obtained when the2,4,5-trichlorophenyl bis (dipropylene glycol) phosphite was replaced by27.2 grams of 2,4,6-trichlorophenyl bis (dipropylene glycol) phosphate.

Example 41 The polyol used in Formulation B was a mixture of 67 grams ofoctakis (Z-hydroxypropyl) sucrose (hydroxyl No. 560) and 53.5 grams oftetrakis (dipropylene glycol) tetrachloro (Bisphenol A) diphosphite.This mixture was kept at 15 C. and there was added 118.5 grams of4,4-diphenylmethane diisocyanate. An exothermic reaction ensued to forma solid, non burning foam. A similar result was obtained when thetetrakis (dipropylene glycol) tetrachloro (Bisphenol A) di-phosphite wasreplaced by 53.5 grams of his (hydroxypropoxypropane) bis (dipropyleneglycol) tetrachloro (Bisphenol A) diphosphonate or by 53.5 grams oftetrakis (dipropylene glycol) tetrachloro (Bisphenol A) diphosphate.

PERTINENT ART Lanham-2,909,559; discloses alkylene glycol bis (2,4-dichlorophenyl) phosphate, and polyalkylene glycol bis(2,4-dichlorophenyl) phosphate.

Hurdis-2,891,985; discloses lower alkyl bis (tetrachlorobisphenol Adiethanol) phosphate.

Toy2,643,265; discloses bis (dialkyl phosphate) ester oftetrachlorobisphenol A.

Weisel2,542,604; discloses tris (pentachlorophenyl) phosphate and alkylbis (pentachlorophenyl) phosphate.

Bereim3,046,296; discloses (p-PBIllZfiChlOIOPhEHYl di lower alkylthiophosphate.

Renner-3,081,333; discloses pentachlorophenoxy (1)- propanol(2)-phosphonic acid di lower alkyl ester (as well as the correspondingdi, tri and tetrachloro or bromo phenyl compounds).

Harris2,828,198; discloses phenoxyethyl) phosphite.

Tolkmith2,668,84l; discloses O-ethyl 0-(2,4,5-trichlorophenyl) methanephosphonate.

Moyle2,599,515; discloses di lower alkyl 2,4,5-trichlorophenylphosphate.

Drake-2,599,375; discloses di lower alkyl 2,4,6-trichlorophenylphosphate.

Turbak-3,072,618; discloses tris 2,4-dichloro-pheny1) phosphite and thecorresponding phosphate.

Hechenbleikner-2,834,798; discloses several tris (dichlorophenyl)phosphites.

Moyle2,170,833; discloses diaryl 2,4-dichloro-phenyl phosphite.

Hechenbleikner-3,147,297; discloses tris (2,4,5-trichloro-phenyl)phosphite.

Friedman-3,142,651; discloses bis dipropylene glycol ester of4-chlorophenyl phosphonic acid. 1

tris (2,4,5 trichloro- R is a polyhalophenyl group wherein the halogenatoms have an atomic weight of 35 to 80;

R and R are hydroxyalkyl;

R is alkylene;

R and R are selected from the group consisting of alkylene andhydroxyalkylene;

x, y and z are selected from the group consisting of zero and a positiveinteger;

R R R and R are selected from the group consisting of alkylene,alkylene-oxyalkylene and alkylene poly- (oxyakylene); and

R is a ring polyhalo substituted alkylidene bisphenol from which thehydroxyl hydrogens have been removed, the halogen atoms have an atomicweight of 35 to 80 and the alkylidene group has 1 to 9 carbon atoms.

2. A phosphonate having the formula R is a polyhalophenyl group whereinthe halogen atoms have an atomic weight of 35 to 80; R and R arehydroxyalkyl;

R and R are alkylene; and

y and z are positive integers.

3. A phosphonate according to claim 2 wherein there are 3 to 5 halogenatoms in the polyhalophenyl group.

4. A phosphonate according to claim 2 wherein there are 3 halogen atomsin the polyhalophenyl group.

5. A phosphonate according to claim 4 wherein-0R and CR are residues ofpolypropylene glycol from which one terminal hydrogen has been removedand the other terminal hydroxyl has been removed.

6. A trihalophenyl dipropylene glycol hydroxypropoxypropane phosphonatewherein the halogen atoms have an atomic weight of 35 to 80.

7. 2,4,6-trichlorophenyl dipropylene glycol hydroxypropoxypropanephosphonate.

8. 2,4,5-trichlorophenyl dipropylene glycol hydroxypropoxypropanephosphonate.

9. A phosphonate according to claim 2 wherein there are 5 halogen atomsin the polyhalophenyl group.

10. A phosphonate according to claim 9 wherein 0R andOR are residues ofpolypropylene glycol from which one terminal hydrogen has been removedand the other terminal hydroxyl has been removed.

11. A pentahalophenyl dipropylene glycol hydroxypropoxypropanephosphonate wherein the halogen atoms have an atomic weight of 35 to 80.

12. Pentachlorophenyl dipropylene glycol hydroxypropoxypropanephosphonate.

13. A phosphonate having the formula HORroO ORnOH where R R R and R areselected from the group consisting of alkylene, alkyleneoxyalkylene andalkylene poly(oxyalkylene) and R is a ring polyhalo substitutedalkylidene diphenol from which the hydr-oxyl hydrogens have beenremoved, the halogen atoms have an atomic weight of 35 to and thealkylidene group has 1 to 9 carbon atoms.

14. A phosphonate according to claim 13 wherein R R R and R are residuesof a poly lower alkylene glycol and R is a residue of tetrahaloisopr-opylidene diphenol.

15. A phosphonate according to claim 14 wherein R R R and R are residuesof polypropylene glycol.

16. A phosphonate according to claim 15 wherein R R R and R are residuesof dipropylene glycol.

17. A phosphonate according to claim 16 wherein the four halogen atomsare all chlorine and are in the 2, 6, 2' and 6 positions.

18. A compound according to claim 17 wherein the hydroxyl groups presentare secondary hydroxyl groups.

19. A phosphonate according to claim 16 wherein the four halogen atomsare all chlorine and are in the 2, 6, 2' and 6' positions.

References Cited UNITED STATES PATENTS 6/1953 Toy 260-930 10/1962Friedman 260-953

1. A PHOSPHONATE HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF